Herbicidal 6-amino-s-triazinediones

ABSTRACT

Compounds of the formula:   WHEREIN X is oxygen or sulfur; R1 is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylmethyl, cycloalkenylmethyl, bicycloalkyl, bicycloalkenyl, bicycloalkylmethyl, bicycloalkenylmethyl, phenyl, substituted alkyl, substituted cycloalkyl, or substituted phenyl; R2 is hydrogen or alkyl; R3 is H, methyl, or ethyl; and R4 is alkyl, alkenyl, alkynyl, or methoxy; and the salts with bases of those compounds wherein R2 is hydrogen, are useful as herbicides. A preferred compound is 1methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione.

United States Patent Lin 1 Sept. 2, 1975 [54] HER-BICIDAL PrimaryE.\'z1n1im'rElbcrt L. Roberts N0. 1 1 N ASSiSltI/IIIi.\'un1i11w'-Czitherine L. Mills [75] Inventor: Kang Lin. Newark. Del.

1 4 [57] ABSTRACT [73] Assignee: E. l. Du Pont de Nemours and Company,Wilmington Del Compounds of the formula:

[22] Filed: June 5, I974 I 21 Appl. No.: 476.552 N Related U.S.Application Data 1 R3 [63] Continuation-impart of Scr. No. 348,321,April 5. CAN

1973, abandoned. which is a continuution-in-purt of 4 Ser. No. 256.249.May 24. 1972. abandoned. R2

[52] U.S. Cl 71/93; 260/2495 wherein X is Oxygen or sulfur; Rl is alkyl.alkenyl [51] Int. Cl. AOIN 9/22 y y cycloalkylg cycloalkenyl y m y y y[58] Field Of Search 71/93; 260/2495 cloalkenyhnethyL bicycloalkyhbicycloalkenyl y cloalkylmethyl, bicycloalkenylmethyl, phenyl.substituted ulkyl, substituted cycloalkyl, or substituted ReferencesCited phenyl; R is hydrogen or alkyl; R is H methyl, or UNITED STATESPATENTS ethyl; and R is alkyl, ulkenyl, ulkynyl, or methoxy; 3501057 41970 Luckenbuugh 71 93 and the Salts with bases of those P wherein3.544.570 12/1970 Timmler m 111. 71 93 x is hydrogenare useful asherbicides- A Preferred 3,682,909 8/1972 Hugemann.... 71/93 X compoundis l-methyl-3-cyclohexyl-6-dimethylamino- 3 835 l33 9/l974 Seckingcr71/93 X s-triazine-2,4( lH,3H)-dione.

18 Claims, N0 Drawings HERBICIDAL 6-A-MINO-S-TRIAZINEDIONES where X is.inter alia. (Cz s)z (C a a I2N"' CROSS-REFERENCE TO RELATED iAPPLICATIONS, I SUMMARY OF THE INVENTION This application is acontinuation-in-pa-rt of applica- This inventionrelates'to novelcompounds of formula tion Ser. No. 348.32l. filed Apr: 5. 197-3; no\\'abanl and their use as herbicides doned. which is. in turn. acontinuation-in-part ot'application Ser. No. 256.249. tiled May 24.I972. now abandoned. The entire disclosure of said applications Ser. ifNos. 256.249 and 348.32l is hereby incorporated by I R A reference. l\ NN BACKGROUND OF THE INVENTION I The invention relates to s-triaxineherbicides. more N R particularly to a novel class of6-amino-s-triazinedioncs l O N and their use as herbicides. u

Neumayer et al.. "Pesticides". Chemical Week. April 2 l2 and 26. I969.lists several commercial and experimental striazine herbicides. Amongthese are two wellknown products. atrazine and simazine: 3U I C1. C1 N NAN 1 3 LN I CH CH I CE CH CH I -CH CH-. H H \03 H H 9 Atraz ine SimazineLuckenbaugh U.S. Pats. Nos. 3.505.323 and whcrfm 3.505.057 teach a classof tetrahvdro-s-triazinones of Sclcctcd from 0t 2 through 8 Curhm momsformula A below. and their use as herbicides. German 3 thmugh 6 cilrhm 3OffcnlcgungSSChrit-t 1961797 discloses a Class of through 6 carbonatoms. cyclemlkyl of 4 through 8 triazinoncs of formula B below. andtheir use as hei'bicmhon mums -P 5 through 8 Cidcs. atoms. c \'cloalk'lmethyl ol 4 through 9 carbon atoms. cycloalkenylmethyl of 6 through 9carbon 49 atoms. bieycloalkyl or bicycloalkenyl of 7 through (A) (B) 1()carbon atoms and bic \cloalkylmethyl or bicycloalkenylmethyl of 8through ll carbon atoms. Q X trimethylcyclohexyl andtetramethylcyclohexyl; (X) R the above alkyl groups substituted with onemethoxy. )k N N ethoxy. methylthio or ethylthio group;

I. R A the above cycloalkyl groups substituted with one I i\ J alkyl of2 through 4 carbon atoms. l through 2 Y N 3 N H 2 methyl groups. Ithrough 2 chlorines or bromines.

one methoxy or one ethos group; and R Q=Sor() X=SorO Q X halogen R,. R;-and R" H or alk \'l Y H.'halogen. alkyl. etc. R and R, ;lll\' \'l Z n lor 2 Chem. Ber. I04. I606 I971 relates to the prepara- Y tion ofs-triazinethiones by cyclocondensation of ethox- H ycarbonylisothiocyanate with amidines. isoureas. isothioureas. and guanidines: H

S wherein u\ Q is hydrogen. fluorine. chlorine. bromine. alkyl of l Ithrough 4 carbon atoms. alkoxy or alkylthio of RN N I through 2 carbonatoms. nitro or a trifluoro /U\ methyl group;

Y is hydrogen. chlorine. or methyl; and H Z is hydrogen or chlorine:

R: is hydrogen; alkyl of 1 through 3 carbon atoms or a cation selectedfrom Na. Li. K (Ca/2 l". ammonium and dimethylammonium;

R, is hydrogen, methyl or ethyl;

R, is alkyl of I through 4 carbon atoms, alkenyl of 3 through 4 carbonatoms, alkynyl of 3 through 4 carbon atoms, or methoxy; and

X is oxygen or sulfur: provided that when X is sulfur. neither R nor R,,is hydrogen.

The invention also includes certain methods for making the above6-aminotriazinediones, use of the 6- aminotriazinediones to controlundesired vegetation, and herbicidal compositions containing the 6-aminotriazinediones.

Preferred are:

a. those compounds of formula I where:

R, is alkyl of 3 through 6 carbon atoms. cycloalkyl of 5 through 8carbon atoms, or cycloalkyl of 5 7 through 8 carbon atoms substitutedwith one methyl group;

R R and R, are methyl; and

X is oxygen or sulfur;

b. those compounds of formula I where:

R, is alkyl of 3 through 6 carbon atoms; cycloalkyl of 5 through 8carbon atoms; cyclopentyl substituted with one methyl group; cyclohexylsubstituted with l or 2 methyl groups: 3-trifluoromethylphenyl;cyclohexenyl; or deeahydronaphthen-l-yl: I

R; and R are methyl;

R, is hydrogen: and

X is oxygen; and

c. those compounds of formula I where:

R, is cyclohexyl substituted with two methyl groups;3-trifluoromethylphenyl; cyclohexenyl: decahydronaphthenl -yl; or

R, is

clohexyl; 2,3-dimethylcyclohexyl: 3,4-dimethyl cyclohexyl;3-trifluoromethylphenyl; 3- cyclohexen- 1 -yl; l-dccahydronaphthyl; 2-methylphenyl; 4-methylphenyl; 3,4- dichlorophenyl: 2,5-dichlorophenyl;2-

chlorophenyl; 3-chlorophenyl; 4-chlorophenyl; Z-fluorophenyl;3-fluorophenyl: 2-methyl-5- chlorophenyl; or 3 chloro-4methylphenyl.

More preferred arethose compounds of formula ,I where R, is cyclopentyl,methylcyclopentyl, cyclohexyl, or methylcyclohexyl; R R and R aremethyl; and X is oxygen.

Most preferred are the following two compounds: 3-cyclohexyll-methyl-6-dimethylamino-s-triazine- 2,4(1H;3H)-di0ne, and v3-cyclopentyll methyl-6-dimethylamino-s-triazine- 2.4(1H.3H)-dione.

DESCR lPTION OF THE INVENTION Synthesis of the Compounds The compoundsof formula I are made by the processes described and exemplifiedhereinafter.

The first method to be described starts with cyanamide and involvesreaction steps 1 through 5 shown below:

(compound I wherein X is sulfur and R;- and R are alk \li wherein: R Rand R are as previously defined. R is hydrogen or alkyl of 1 through 4carbon atoms. R g is that part of R limited to alkyl. R';, is that partof R limited to alkyl. M is alkali metal. and Z is iodide or The processof preparation of methyl cyanocarbamate (compound 3) from cyanamide(compound I) and methyl chloroformate (compound 2) is described in US.Pat. No. 3.657.443 (Equation 1). 5

An aqueous solution of the sodium salt of compound 3containing from to35% of 3. preferably to is reacted at lO to C., preferably 25 to 45C..with 0.9 to 1.4. preferably 1.0 to 1.2. molecular equiva Ients of analkylating agent 4 (for example, dimcthyl sulfate) during a period of 2to 16 hours. preferably 4 to 8 hours (Equation 2). As the reactionproceeds at second phase of compound 5 forms. After the reaction hasproceeded for the desired time the upper layer of compound 5. whichcontains some water. is separated and the lower aqueous layer iscontacted with an organic solvent selected from methylene chloride.dichloroethane. triclene. benzene. toluene and xylene: toluene ispreferred. Other dialkyl sulfates (or alkyl halides) can be used insteadof dimethyl sulfate. the sulfates being preferred for economic reasons.

The extract and the upper layer are analyzed for compound 5 by gaschromatography and added to an aqueous solutioncontaining 15 topreferably 25 to 509: of the hydrochloride or sulfate of compound 6.preferably the sulfate (Equation 3). The mole ratio of amine salt tocompound 5 can be from l to 3. prefera My [.5 to 2.5. The extractionsolvent used (cg. tolu ene) is removed by either azeotropic or simpledistillation.depending on the boiling point. The residual aqueousmixture is then agitated for from 3 to 10 hours at 50 to l 10C..preferably to C. (Equation 3). Higher temperatures require shorterreaction times and vice versa.

The resulting reaction mass contains compound 7 and byproducttrisubstituted guanidine as well as unreacted compound 6. all present assalts. Before proceeding with the reaction of compound 7 with compound 8it is necessary to liberate the free bases and remove the excesscompound 6 to prevent the formation of byproduct urcas. This operationcan be effected by adding 50% aqueous sodium hydroxide equivalent to theamount of compounds 6 and 7 present. as determined by gaschromatographic analyses. and extracting with an organic solvent such asmethylene chloride. followed by distilling a portion of the organicsolvent to remove excess compound 6. or by removing compound 6 directlyfrom the aqueous solution by distillation or by stripping with an inertgas after first adding base to form the free amine. The latter procedureis preferred. Compound 7 is relatively unstable in aqueous solution whenpresent as the free base and tends to decompose into the correspondingtrisubstituted guanidinc. The rate of decomposition is directlyproportional to pH and temperature. Therefore. when removing excesscompound 6 by direct distillation or stripping from water it isadvantageous to use a vacuum and to perform the operation as rapidly aspossible.

The above described aqueous distillation procedure can be operatedbatchwise or continuously. It is preferred to carry out the operation ina continuous manner so that the exposure of compound 7 to high temperature and high pH is reduced to a minimum. This is accomplished byadding aqueous alkali metal hydroxide to the product from reaction 3 ina pipeline reactor or by running the product and the alkali metalhydroxide into a small agitated vessel with a short holdup time. from tominutes. preferably 0 to 2 minutes. If the concentration of amine saltused is such that sodium salt precipitates during this neutralizationadditional water must be added to maintain this salt in solution. Theoverflow from this vessel is fed to a distillation column operated undervacuum. The column is heated by feeding steam into the bottom; compound6 and water are taken off as distillate (overhead) and an aqueoussolution of compound 7 and trisubstituted guanidine as bottoms.

The conditions under which the column can be operated are numerous anddepend to some extent on the nature of compound 6. However. in general.conditions are selected so that the temperature of the feed to thecolumn is not over 50C. This necessitates cooling the product fromequation 3 to approximately C. before adding the caustic. The column isoperated at a pressure of 25 to 300 mm of Hg preferably 50 to l50 mm andthe amount of steam fed to the bottom of the column is adjusted suchthat the amount of water taken overhead along with compound 6 isequivalent to 5 to 25/( of the weight of the reaction mass from equation3.

The bottoms from the above distillation are fed into a hold tank whichis maintained at a pH of 5 to 7 by the continuous addition of eithersulfuric or hydrochloric acid; sulfuric is preferred. The concentrationof compound 7 in'the neutralized solution is maintained at l5 to 50%.preferably 20 to The concentration will depend upon'the strength of thesalt solution of compound 6. base and acid solutions employed in theprevious steps. and the amount of concentration or dilution whichoccurred during the distillation. The temperature of this solution ismaintained at 25 to C.. preferably 25 to 35. by either cooling thebottoms in a continuoustypc cooler before neutralization or by coolingthe neutralization vessel itself.

Reaction 4 is performed by preparing a mixture of the above solution anda solvent such as benzene. chlorobenzene. toluene or xylene; toluene ispreferred. The amount of solvent added should be sufficient to dissolvethe amount of compound 9 which will be formed. Generally the amount ofsolvent used is about 7 to 10 times the amount of compound 7 present inthe aqueous solution. I

An amount of compound 8 which is stoichiometrically equivalent to 85 to100%. preferably 92 to 9871, of the compound 7 present in the aqueouslayer is now added and with good agitation the addition of 5071 aqueouscaustic is started while the temperature is maintained at 5 to C..preferably 5 to 35C. by external cooling. The caustic addition is madeas rapidly as heat can be removed to maintain the desired temperatureand is continued until an amount stoichiometrically equivalent to theamount of acid used in neutralizing compound 7 has been added. If asolid phase of a sodium salt is now present. sufficient water should beadded to dissolve it. The reaction is'allowcd to continue after thecaustic addition is complete until the pH of the aqueous solution isnearly constant. This requires an addition time of l to 3 hours.Alternately, compound 8 and theaqueous caustic can be added simultaneously while the pH of the reaction mass is maintained at 9 to 10.preferably 9.3 to 9.7. during 1 to 4 hours. preferably 2 to 3. Theaqueous sodium hydroxide' addition is then continued until the pH isnearly constant. The agitation is stopped and the layers allowed toseparate. The lower aqueous layer is removed and the upper organic layeris evaporated at a pressure of 50 to 760 mm/Hg, preferably to 300 mm/Hg.until a clear distillate is obtained (indicating that all water has beenremoved).

The residual solution or slurry containing compound 9 is cooled. ifnecessary, to 2545C., while anhydrous amine 6 (for example.dimethylaminc) is added, either as a gas, or a liquid. It is preferredto add the amine 6 at 2535C.. but higher or lower temperatures can beused depending on the solubility of amine 6 in the particular solvent.It is important to have at least 1.0 and, preferably, [.0 to 2.5 molesof amine 6.

Next the ring closure catalyst (compound I0) is added (Equation 5). Thecatalyst is an alkali metal alkoxide (or hydroxide) and it may be addedeither as a dry solid or as a solution in the alkanol. Dry sodiummethoxide or a solution of sodium methoxide in methanol is a preferredcatalyst. The amount of catalyst needed is from 0.1 to 5.0 mole percentof compound 9. Higher concentrations are not desirable because sidereactions begin to intervene. A preferred concentration of compound 10is from L0 to 2.0 mole percent of compound 9. The temperature is notcritical and the and the-solution may be cooled if a lower temperatureis required to retain amine 6. It is critical that the amine 6 remainpresent until ring closure is about complete.

After the catalyst is added. the reaction mass is held for 0. l to 2.0hours to insure completion of the ring closure. The reaction is rapidand normally is about complete in less than 1.0 hour.

The amine 6, byproduct methanol. and part of the solvent are thenremoved by distillation, either at atmospheric or reduced pressure.Water is then added and the remainder of the solvent is removed byazeotropic distillation. The overhead water may be discarded or returnedto the system, whichever is desirable. The amount of water remainingin-the residue is not critical and may range from 0.1 to 5 or more partsper part of compound 1 1. depending on how compound 1 l is to beisolated. Isolation can be by crystallization followed by filtration orcentrifugation. by spray-drying, by phaseseparation to remove most ofthe water, or by other conventional methods. I

Alternatively. compound l l"can be recovered without distillation of allthe methanol, amine 6 and solvent. If a poor solvent for compound l 1,such as hexane. is added to the reaction mixture. compound 1 1 willprecipitate and can be recovered by conventional methods.

The following examples further illustrate this method for synthesis ofcompounds of this invention.

In the examples all parts are by weight and all temperatures indcgreescentigrade unless otherwise indicated. Refractive indicesrecorded as n,,- are values at 25C.

EXAMPLE 1 A. Synthesis of N-Methoxyearbonyl-N-methylcyanamide (Equations1 and 2) i To a solution of 504 parts of a 50' aqueous cyanamidesolution in 825 parts of water at 25 are added during a period of 90minutes and at a pH of o.*)-7.l simultaneously 572 parts of methylehloroformate and 945 parts of a 50 aqueous sodium hydroxide solution.As the addition of the reactants progresses. the temperature of thereaction is allowed to rise to 53-55 and is maintained within that rangeby cooling. When the addition is complete. the reaction mass is cooledto 25. whereupon crystallization of the sodium salt ofmethoxycarbonyleyanamide occurs. Dimethyl sulfate (775 'parts) is thenadded. and agitation of the reaction mass is continued while maintainingthe pH at 7-7.1 by a dropwise addition of about 25 parts of a 50%aqueous sodium hydroxide solution. After (1.5 hours. the resultingtwo-phase solution is repeatedly extracted with methylene chloride andthe extract is dried. One half of 'the methylene chloride extract isthen evaporated 'under vacuum. and the residue is distilled at 50/0.5mm. There is obtained 237.6 parts of N-'methoxycarbonyl-N-methylcyanamide (69.5)? yield).

By using the appropriate amount of diethyl sulfate. dipropyl sulfate ordiisopropyl sulfate the following intermediate cyanamides can beprepared in a similar manner.

N-methoxycarbonyl-N-ethylcyanamide N-methoxycarbonyl-N-propylcyanamideN-methoxyearbonyl-N-isopropyleyanamide B. Synthesis ofN-methoxycarbonyl-N.N'.N'-trimethylguanidine (Equation 3) A solution of339 parts of dimethylamine hydrochlo- 'ride in 500 parts of water isheated to 50. and the remaining half ofthe above methylene chlorideextract is added to it gradually. while at the same time the methylenechloride is removed by distillation. The resulting two-phase mixture isthen heated for approximately 20 hours at 80. after which time thestarting N- 'methoxycarbonyl-N-methylcyanamide has nearly completelydisappeared. The solution is then cooled to 0, and 336 parts of a 50%aqueous sodium hydroxide solution is added. Repeated extraction of thereaction solution with methylene chloride and evaporation of themethylene chloride under vacuum gives 228.6 parts of crudeN-methoxycarbonyl-N.N.N-trimethylguanidine of 84.4% purity. from whichthe pure product is isolated by distillation at 72/0.5 mm.

By the above procedure using equivalent.molecular weight amounts of theappropriate amines and appropriate N-methoxycarbamoyl-N'-alkylcyanamidesthe following intermediate guanidines can be prepared.

TABLE I N-methoxyearbonyl-N-methyl-Nethyl-N'- methylguanidineN-methoxyearbonyl-N-methyl-N '-isopropyl-N methylguanidineN-methoxycarbonyl-N-mcthyl-N -butyl-N methylguanidineN'mcthoxycarbonyl-N-methyl-N '-allyl-N methylguanidineN-nlethoxycarbonyl-N-methyl-N -propargyl-N methylguanidineN-methoxyearlmnyl-N-methyl-N '-methoxy-N methylguanidincN-methoxycarbonyl-N-ethyl-N'. N'-dimethylguanidincN-methoxycarlmnyl-N-isopropyl-N'. N- dimethylguanidineN-methoxycarbonyl-N-n-propyl-N N dimethylguanidinc (T. Synthesis ofMethyl N-(N-cyclohexylcarbamoyl-N'. N -dimethylamidino)-N-methylcarbamate Equation To 14.8 parts of the above crudeN-methoxycarbonyl-N.N'. N'-trimethylguanidine in 50 parts of methylenechloride is added 1 1.0 parts of eyclohexyl isoeyanate. The solutiontemperature reaches the boiling point. and when the temperature hasfallen to 25. the solvent is evaporated under vacuum to give an oil.which crystallizes w-hen triturated with ether. Recrystallization from amixture of carbon tetrachloride and petroleum ether gives pure methylN-(N-cyclohexylcarbamoyl-N. N-dimethylamidino )-N- mcthylcarbamate. nrp.9394.

TABLE ll Following the general method of Example 1C. using theappropriate isocyanatc as isothiocyanate as reactants with theappropriately substituted methoxycarbonylguanidine. the followingcompounds can be preparedv Methyl N-( N-cyclopentylcarlmmoyl-N'. Ndimethylamidino)-N-methylcarbamate Methyl N-[ N-(Z-methyleyclohexylcarbamoyl )-N. N- dimethylamidino l-N-methylcarbamateMethyl N-{ N-( 3-methylcyclohexylcarlmmoyl l-N N dimethylamidino|-N-mcthylcarbamate Methyl N-( N-cycloheptylcarbamocyl-N Ndimethylamidino )-N-methylcarbamate Methyl t N-( N-cyclooctylcarbamoyl-N'N dimethylamidino )-N-methylcarbamate Methyl N-(N-cyclohexylearbamoyl-N N dimethylamidino )-N-ethylcarbamate Methyl N-(N--cyclohexylcarbamoyl )-N N dimethylamidino )-N-n-propylcarbamateMethyl N-( N:cyclohcxylcarbamoyl-N N dimethylamidiim)-N-isopropylearbamate Methyl N-( N-cyclohexylcarbamoyl-N '-butyl-Nmethylamidino )-N-methylcarbamate Methyl N-( N-cyclohexylcarbamoyl-N'-allyl-N methylamidino N-methylcarbamate MethylN-(N-cyclohexylcarbamoyl-N'-propargyl-N'- methylamidino)-N-methylcarbamate Methyl N-( N-cyclohexylcarbamoyl-N-methoxy-Nmethylamidino )-N-methylcarbamate Methyl N-(N-cyclopentylthiocarbamoyl-N N dimethylamidimi )-N-methylcarbamatcMethyl N-( N-cyclohexythioearbamoyl-N. N'- dimethylamidino)-N-methylcarbamate. m .p.

Methyl N-[N-(p-fluorophcnylthiocarbamoyl)N'. N'- dimethylamidino]-N-methylcarbamate. m.p.

Methyl N-[ N-( m-fluorophenylthiocarbamoyl )-N N dimethylamidinol-N-methylcarbamate Methyl N-[ N-( sec-butylthiocarbamoyl )-N'.Ndimethylamidino I-N-methylcarbamate 1 1 MethylN-(N-neopentylthiocarlmmoyl-N. N'- dimethylamidino )-N-methylcarbamateMethyl N-( N-norbornylthiocarbamoyl-N N dimethylamidino)-N-methylcarbamate D. Synthesis of l-Methyl-3-cyclohexyl-6-dimethylamino-s-triazine- 2.4( 1H.3H)dione (Equations 2. 3. 4. 5)

A 1071 stoichiometrie excess of dimethyl sulfate (906 parts) is added at25 with agitation to 3050 parts of an aqueous solution containing 797parts of the sodium salt of compound 3 which has been adjusted to pH 7with 50% aqueous sodium hydroxide. The reaction is allowed to continuefor 6 hours while the temperature is maintained at 25 by externalcooling and at pH 7 by the addition of 50? aqueous sodium hydroxide asrequired. During the reaction a separate phase of compound 5 (R CH.) isformed.

When the reaction is about complete the agitation is stopped and thelayers allowed to separate. The upper layer of compound 5 (R- CH isremoved and the lower aqueous layer extracted with 2000 parts oftoluene. The upper layer and the extract are added to 3300 parts of anagitated solution containing 920 parts of dimethylammonium sulfate in avessel equipped for solvent removal. The resulting mixture is heated to90 and vacuum applied to remove the toluene by azeotropic distillation.The distillation requires one hour and the reaction is continued for anadditional 5 hours at 90. The reaction mass is then cooled to 30.

The above solution (3440 parts) is analyzed for dimethylamine andcompound 5 (R =CH;,) by gas chromatography and found to contain 264parts of dimethylamine and 625 parts of compound 7 (R'- =R,,=R.,==CH;;).The solution is then fed into a stirred vessel along with 50% aqueoussodium hydroxide at a rate of 28.6 parts of solution and 6.04 parts of5071 aqueous sodium hydroxide per minute. (This amount of sodiumhydroxide frees compounds 6 and 7 from their salts; R' =R;;=R =H Theresidence time in this vessel is two minutes. The effluent from thisvessel is fed into the top of a packed column operated at 100 mm/Hgabsolute pressure with total take-off. Atmospheric-pressure steam is fedinto the bottom of the column at a rate such that the volume of Hdistilled over is parts/minute. The stripped solution that exits thebottom of the column (into a vessel containing 800 parts of water) iscontinuously neutralized to pH 6.5 with concentrated sulfuric acid andcooled 0 30 by external cooling.

When the distillation is complete the vacuum is broken and 4700 parts oftoluene and 470 parts of cyclohexyl isocyanate (approximately 90% of thetheoretical amount) are added to the neutralized still bottoms and 50%aqueous sodium hydroxide equivalent to the amount of sulfuric acid usedin neutralizing the still bottoms is added during one-half hour whilethe temperature is maintained at 30 by external cooling.

The reaction is allowed to continue for an additional 3 hours until thepH becomes nearly constant at 8.8. The temperature is adjusted to 34 andmaintained for 10 minutes after which time the agitator is turned offand the layers allowed to separate. The lower aqueous layer is removedand the toluene layer is distilled at 100 mm of Hg until a cleardistillate is obtained.

Dimethylamine (375 parts) is sparged into the residue while thetemperature is maintained at by external cooling. Then 15.9 parts of a25% solution of sodium methox ide in methanol is added with goodagitation. 'lihe'rea'ction is' slightlyexothermic and thetemperatureliner eases during 1 5 minutes to 35. The r'eac tion isallowed to continue for an additional one-half hour. The solutionisthenconcentrated at mm of Hg until 40 00parts oftoluene have been removed.Water (1900 parts) i's fadde d and distillation is continued untiltoluene removal is complete. Water taken overhead is returned tothestill pot via a water separa-' tor.

The residue is cooled to 15 and stirred until precipitation of theproduct is complete. The solids are collected by filtration and dried togive 745 parts (45.37: based on compound 3) of compound 1 l (R=cyclohcxyl; R;,=R =R =methyl), m.p. 97l00.5. The aqueous filtrate canbe recycled to lessen loss of product l l. 7

An alternate isolation of compound 1 1 from the aqueous solution is asfollows: The aqueous residue from the distillation is heated to 60. Thisresults in the formation of a twophase system. The lower organic layeris separated from the upper aqueous layer. The organic phase amounts toI070 parts and contains 762 parts of compound 11. The water phasecontains 77 parts of compound 1 l and can be recycled back to the stillpot to obtain higher overall recoveries. I

The following s-triazinediones are prepared by cyclization of theappropriate methyl N-(N-substituted c'a r bamoyl or thioearbamoyl-N,N'-dialkylamidino') -l l-- alkylcarbamate by the above procedure.

TABLE Ill 1-Methyl-3-(sec.butyl)-o-dimethylamino-s-triazine-4- thio-2.4(lH.3H)-dione 1-Methy|-3-neopentyl-6-dimethylamino-s-triaZine-4-thio-2.4(1H, 3H)-dione l-Methyl-3-( 2-norbornyl)-6-dimethylamino-s-triazine- 4-thio-2,4( 1H. 3H)-dione:;

E. Alternate Synthesis of Methyl N-( N-cyclohexylcarbamoyl-N N'-dimethylamidino -N-meth ylcarbamate (Equation 4) v A solution of thesulfatesalt of 7 as prepared in Example 1D is mixed with 4700 parts oftoluene. and 470 parts of cyclohexyl isocyanate is added during 2 hourswhile the pH is maintained at 9.5 by the continuous addition of 50%aqueous sodium hydroxide. The sodium hydroxide addition is continued foran additional '3 hours until the pH becomes about constant at 9.5. Thetemperature is maintained at 30 throughout the reaction. The reactionmixture is worked up as in Example 1D to give methylN-(N-cyclohexylearbamoyl-N'. N'- dimethylamidinol-N-methylcarbamate inabout the same yield.

Equations 1/: and 2!) describe how to make'those compounds of thisinvention where X is sulfur.

Equation lb: The methoxycarbonylguanidine derivative 7h reacts with anisothioeyanate 12) in an inert solvent (such as tetrahydrofuran) atabout room temperature to 100 for about 1 to 12 hours to form the mcthoxycarbonylallophanimidate 13. This intermediate can be isolated byevaporation of the solvent and further purified. if desired. byrecrystallization; or the intermediate can be used directly, withoutisolation. in the next step (212).

Equation 2h: The methoxycarbonylallophanimidatc l3 in an inert solvent(such as toluene) is treated with an alkali metal ulkoxidc or hydroxide(such as the methoxide of hydroxide of sodium or potassium) and themixture heated to effect cyclization of compound l3 to thetriazine-4-thione 14. Compound 14 can be isolated by cooling thereaction mixture and filtering off precipitated 14. If desired. 14 canbe further purified by recrystallization from an inert solvent (such asethyl acetate)v EXAMPLE 2 Synthesis ofl-Methyl-3-cyclohexyl-6-dimethylaminos-triazine-4- thio-2.4-( lH.3H)-dione A mixture of 100 parts of N-mcthoxycarbonyl-N.N'.N'trimcthylquanidine. as prepared in 18. 89 parts of cycloheXylisothiocyanate and 0.5 parts of dibutyltin dilaurate is heated for 8hours at 70 in 1000 parts of toluene. The clear. yellow solution is thenheated to reflux and 50 parts of toluene is distilled out. A l2.5-partaliquot of 0.5M sodium mcthoside in methanol solu tion is added over a30-minute period. allowing toluene to distil out of the reactionmixture. After the addition is complete. additional toluene is distilledout until 500 parts of toluene have been removed. The reaction mixtureis cooled and the resulting pale yellow product. 1-

methyl-3-eyclohexyl-o-dimcthylamino-s-triazine-4- thio-2.4( lH. 3H)-dionc. crystallizes. Filtration and drying affords 1 [3 parts ofproduct. m.p. 2l()-2l2.

The intermediate methyl l\l(N-cyclohexylthiocarbamyl-N'.N-dimethylamidino)-N-methylcarbamate can be isolated by removing thetoluene at reduced pressure and crystallizing the crude solid from ethylacetate giving the purified intermediate. m.p. l22l23.

in some cases it is not necessary to add the base (sodium methoxidc) toeffect cyclization. for example to the first two triazine-4-thioneslisted below.

Similarly. the following compounds can be prepared using the appropriatereagents.

TABLE IV l-Methyl-3-ethyl-6-dimethylamino-s-triazinc-4-thio- 2.4( lH.3H)-dione. m.p. l39-l4() l -Methyl-3-( n-butyl)-b-dimethylamino-s-triazine-4- thio-2.4( lH. 3H)-dione m.p. l24l2(il-Methyl-3-phenyl-b-dimethylamino-s-triazine-4-thio- 2.4( 1H. 3H)-dione.mp. 209 21 l l-Methyl-3-( o-fluorophenyll-(w-dimethylamino-s-triazine-4thio-2.4( lH. 3H)-dione. m.p. 22()22l l-Methyl-3( m-fluorophenyl )-6-dimethylaminos-triazine-4-thio-2.4( lH.3H)-dione. m.p. 2()4-2()6 l-Methyl-3-( p-fluorophenyl)-6-dimethylaminos-triazine-4-thio-2.4( lH. 3H)-dione. m.p. 224226 l-Methyl-3-( Z-methylcyclohexyl )-6-dimethylamino-stria2ine-4-thio-2.4(lH. 3H )-dione l -Methyl-3-( 3-methylcyclohexyl)-6-diemthylamino-striazinc-4-thio-2.4( lH. 3H )-dionel-Mcthyl-3-cycloheptyl-6-dimcthylamino-s-triazine4- thio-2.4( lH.3H)-dione l -Methyl-3-cyclooctyl-(i-dimethylamino-s-triazilie-4-thio-2.4( lH. 3H)-dione l-Methyl-3 cycloheXyl-6-( N-methyl-N-butylamino)-striazine-4-thio-2.4( l H. 3H )-dione l-Methyl-3-cyelohexyl-6-(N-mcthyl-N-allylamino )-striazine-4thio-2.4( l H. 3H )dione Analternative method for preparing the compounds of this invention startswith a Z-methyl-Z- thiopscudourea salt such as the sulfate orhydrochloride. A schematic representation of this method is shown byequations 6 through [2.

R,. R'- R;;. R R. M and Z are as previously LlCfllTCtl.

A suspension or solution of compound 14 is made in the selected solventand treated with methyl chloroformatc (Equation 6) or an isocyanate offormula R NCO (Equation 611) until the reaction is complete. Theproduct. a l-carbomethoxy2-methyl-2-thiopseudourea (compound 15) or al-cyclohexyl--l-methyI-4-thiopseudobiuret (compound l5a) is treated withan isocyamate of formula R,NCO Equation 7) or methyl chloroformate(Equation 7a) to give compound lo. A solution of compound 16 in asuitable solvent is treated with an alkali metal alkoxide to give thesalt 17 (Equation 8). A solution or slurry of compound 17 in a selectedsolvent is reacted with an alkylating agent to give compound 18(Equation 9). A suspension or solution of compound 18 in a selectedsolvent is treated with an amine (6) to give compound ll. The product. astriazine-2.4( lH. 3H )-dione. can be isolated by conventionaltechniques as described above in the discussion of Equation 5.

In order to make those compounds of this invention where R is hydrogen.the reactions of Equations 1 l and 12 are carried out. Compound 17 isacidified with a mineral acid to compound 19 (Equation 1 l which is thenreacted in Equation l2 with an amine as described above for compound 18.The product formed is an amine salt 21 which can be used in the methodsof this invention or can be'acidified to give compound 22. Compound 22will react with appropriate bases (such as ammonia. dimethylamine. andthe hydroxides of lithium sodium. potassium and calcium) to give thesalts of this invention.

The solvents which can be used in these reactions are water, toluene.benzene. xylenes. monochlorobenzene. nitrobenzene. methylene chloride,triclene. Percelene or mixtures of these organic solvents with water.i.e.. the solvent need not be anhydrous.

With the above solvents it is practical to use a ratio of compound 14 tosolvent such as 1:3 to 1:10. prefera bly from 1:3 to 1:6. Most preferredamong this group of solvents in view of their lower cost and greatersuitability for use in operation of this process are water, toluene.xylene and benzene.

The most preferred solvent for the conversion in Equation 6 is water.Mixtures of water and the organic solvents listed above can be usedfWiththe above solvents it is practical to use a ratio of water: organicsolvent of 1:1 to 1:6. most preferably l'zl'to 1:2.

The two-solvent system is most preferred for the reaction in Equation63, since the isocyanate. 8 reacts with water to form undesiredby-products. v

Yield of product l51 from isocyanate could be seriously reduced by theseside reactions.

The ratios of compounds l4:? and l-'l:8 may be varied from l:0.l to 1:3.preferably from l:0. to 1:2. most preferably 1:1 to l:l.3.

The reactions 6 and bu can be carried out from l0C. to 50C. butpreferably from 0" to 30C. and most preferably from 0 to 25C.

The pH in reaction o. (m and 71! can be varied preferably from 6.5 to ll and most preferably from 7 to 8.5.

The order of addition of reagents methyl chloroformate and isocyanatc RNCO vs. addition of aqueous base can be varied. The methyl chloroformateor isocyanate can be added first. followed by the aqueous base. Butpreferred is the simultaneous addition of methyl chloroformate orisocyanate and the aqueous base. The base can be selected from Li. Naand K hydroxide. The strength of the base to be added can vary from -50%but the higher concentration of base is most preferred because of thelower reaction volume for a given amount of product.

This simultaneous addition of methyl chloroformate or isocyanate R,N(Oand 50% aqueous base gives a higher yield of product l5 or l5u becauseof the controlled pH conditions and shorter contact time with waterrequired for completion of reaction.

The reactions 7 and 7a are preferably carried out between 0 and 50C. andmost preferably between l5 and 35C.

The ratio of methyl'chloroformate to l5u can be 1:1 to 4:1. preferably:1 to 3: I. most preferably 2:] to 2.5: l. The ratio of isocyanatc to 15is preferably l:l.l to 121.5 and most preferably l:l.05 to 1:1.15 in theinterest of obtaining a high percentage conversion of compound 15 tocompound 16 without. the use of an unneeded excess of isocyanate or longreaction time.

The reaction time required for nearly complete reaction is preferably0.5 to 12 hours for both Equations 6:! and 711 and most preferably 1 to4 hours. The reaction time is dependent on the nature and amount ofsolvent and reactants. temperature and type of mixing used.

The reaction time acquired for addition of methyl chloroformate orisocyanate is not critical and may vary from 0.1 to l0 hours. preferablyfrom 0.1 to 4 hours and most preferably from 0.25 to 1.5 hours.

The compound 16 is preferably treated with 0.6 to 1.3 equivalents ofalkali metal alkoxide and most preferably with 0.9 to l.] equivalents.The alkoxide can be used as the pure base or preferably as a solution ina suitable solvent and most preferably as a l5 to solution in thecorresponding alcohol.

The solution of compound lo can be cyclized to compound l7 by use of analkali metal hydroxide but an alcoholic solvent must be added todissolve the hydroxide before cyclization occurs.

The cyclization of compound l6 to compound 17 (Equation 8) takes placepreferably at 25 to 70C. but most preferably at to Cv The removal ofsolvent to give a slurry of compound 17 can be carried out under reducedpressure or at atmospheric pressure at a temperature of C. to 135C. butmost preferably from to 50C. under reduced pressure and from 65 to 100C.at atmospheric pressure.

The alkylation of compound 17 (Equation 9) with alkylating agent 4 (Zhalogen. alkysulfate) can be carried out in a solvent such as water.toluene. benzene. xylene. chlorobcnzene. nitrobenzene. acctonitrile.trielene or perclene.

The preferred solvent is water because of lower cost. simplicity ofprocess operation and case of isolation of the product 18. The productin this case can be isolated by filtration and drying or may be useddirectly as a wet solid in the next reaction by suspension in an organicsolvent and removal of water by azeotropic distillation.

In the case where a dialkyl sulfate is used to alkylate compound 17. thepH of the aqueous solution or slurry should be maintained preferablybetween 7 and ll.5 and most preferably from 9-l0.5 to avoidacidification of compound 17 to give compound 18 where R: is H.

The ratio of alkylating agent to compound 17 is preferably 0.8 to l to1.5 to l but most preferably 1.1 to 1.3:1. The reaction can be carriedout at a temperature from 15 to 135C if in an organic solvent and mostpreferably between 25 and 80C.

When water is used as a solvent the preferred temperature range isl5-80C and the most preferred is 2540C.

The conversion of the 6-methylthio-s-triazine-2.4- lH. 3H)-dione(compound 18) to the 6-amino-striazine-2.4-( lH. 3H)-dione l 1 can bepreferably carried out in a solvent selected from toluene. xylene,benzene. monochlorobenzene. triclene. perclene. nitrobenzene. methylenechloride and 1.2-dichloroethane.

The most preferred solvent is toluene.

The preferred ratio of compound 18 to the amine is preferably 1:1 to 1:6and most preferably. because of complete conversion to ll and shorterreaction time required. 1:2 to 1:3. The amine in selected cases can beused as the solvent.

The conversion of compound 18 to compound ll can be carried out attemperatures from 5 to 135C. but most preferably from 25 to 60C.

The following examples illustrate the methods of Equations 6 through l2.

EXAMPLE 3 A. Synthesis of Methyl N( l-arninol -methylthiomethylene)-carbamate (Equation 6) To a solution of 69.5 parts of 2-methyl-2-thiopseudourea sulfate and 47 parts of methyl chloroformate in 1000parts of water at 0 is added dropwise. 56.9 parts of potassium hydroxidein 200 parts of water. The reaction mixture is stirred at roomtemperature for 3 hours and then extracted with methylene chloride. Themethylene chloride extract is dried and the solvent evaporated on arotary evaporator to give 45 parts of methyl N-(l-amino-l-methylthiomethylene)carbamatc. m.p. 7277.

B. Synthesis of Methyl 4-isopropyl-n-mcthoxycarbonyll-thioallophanimidate (Equation 7) Seventy-four parts of methyl N-(l-amino-lmethylthiomethylene)carbamate and 47 parts of isopropylisocyanate in 300 parts methylene chloride are stirred overnight. Thesolvent is evaporated on a rotary evaporator to give l 13.6 parts ofmethyl 4-isopropy l-N- methoxyearbonyll thioallophanimidate. m.p.

Similarly are prepared the compounds in Table V.

TABLE V Methyl 4-cyclopentyl N-methoxycarbony ll -thioallo-. phanimidateMethyl -l-cyclohexyl-N-methoxycarbonyll -thioallophanimidate. m.p. -86Methyl 4-( 2-methylcyclohcxyl )-N-methoxycarbonyll thioallophanimidateMethol 4-( 3-methylcyclohexyl )-N-methoxyearbonyll thioallophanimidate.I p, Methyl 4-cyclohcptyl-N-methoxycarbonyll -thioallophanimidate YMethyl -4-( 3.5 dimethylcyelohesyl )-N- methoxycarbonyll-thioallophanimidatc Methyl 4-phenyl-N-methoxycarbonyll-thioallophanimidate I Methyl 4-( p-chlorophenyl )-N-methoxyearbonyll -thioallophanimidate. m.p. l27l28 Methyl 4-( 3-chlorocyclobutyl)-N-methoxycarbonyl l thioallophanimidate. m.p. l73-l74.4 Methyl 4-(l-methylcyclopentyl)-N-methoxycarbonyll-thioallophanimidate Methyl 4-(p-methylthiophenyl )-N-methoxyearbonyll thioallophanimidate Methyl4-cyclohexylmethyl-N-methoxycarbonyll -thioallophanimidate. m.p. l32l 34Methyl 4-no rbornyl-N-methoxycarbonyl-l -thioallophanimidate C.Synthesis of 3-lsopropyl-6-methylthio-s-triazine-Z.4( 1H, 3H )dione(Equations 8 and l l One hundred parts of methyl 4-isopropyl-N-methoxycarbonyl-lthioallophanimidate is refluxed for 1 hour with 27parts of sodium methoxide in 200 parts methanol. The methanol isstripped on a rotary evaporator and the residue dissolved in 200 partsof water. The aqueous solution is neutralized with hydrochloric acid.the solid filtered off and dried to yield 55 parts of3-isopropyl-6-methylthio-s-triazine-2.4( lH.3H)-dione. m.p. l88-l9().

By the above method appropriate thioallophanirnidates can be cyclized tothe triazinediones illustratedlithium salt.

G. Synthesis of l-Methyl-3-isopropyl-o-dimethylamino s-triazine- 2.-1(lH.3H)-dione (Equation 10) A solution of ll) parts ofl-methyl-3-isopropyl-omethylthio-s-triazine-Z 4( lH.3 H )-dione in 100parts of tetrahydrofuran at is saturated with dimethylamine. Thereaction'is allowed to warm to room temperature and stand overnight. Thesolvent is evaporated and r the residue triturated with ether to afford9 parts of lmethyl-3-isopropyl-o-dimethylamino-s-triaxine- 2 4)lH3H)-dione. m.p. l()4l()o.

EXAMPLE 4 Modified route for compounds with a bulky group is in the3-position (R in Formula I). using methyl chlorothiolformatel-Methyl-3-( tert-butyl )o-dimethylamino-s-triazine- 2.4( lH.3H)-dione.[Equations 6a. 7a(modified s,9 10

To a solution of 278 parts of Z-methyl-Z- thiopseudourea sulfate in 2000parts of 50% aqueous methanol at 0 is added dropwise 176 parts of 5071sodium hydroxide. followed by 180 parts tert-butyl isocyanate in 400parts tetrahydrofuran. The solution is partially evaporated on a rotaryevaporator and the slurry filtered to yield. after drying. 180 parts ofmethyl 4- (tert-butyl l -thioallophanimidate, m.p. l ()2 l 04.

To a solution of 1 13.4 parts of the above compound and 80 parts oftriethylamine in l()()() parts methylene chloride at 0 is added dropwise66 parts methyl chlorothiolformate in 100 parts of methylene chloride.The solution is stirred overnight. washed once with water. dried andevaporated to provide 76 parts methyl 4-( tert-butyl)-N-methylthiolcarbonyll -thioallophanimidate. m.p. l()2l()5.

Fifty parts of the above compound is refluxed for one hour with 30 partsof sodium methoxide in 500 parts of methanol. The reaction mixture isthen cooled and the methanol is stripped on a rotary evaporator. Theresidue is washed with ether to provide 30 parts sodium 3- (tert-butylj-6-methylthio-s-triazine-2.4( lH. 3 H )-dione.

Twenty-four parts of sodium I 3-(tert-butyl)-6-methylthio-s-triazine-Z,4( lH,3H)-dione and 155 parts of methyl iodideare refluxed overnight in 200 parts of acetonitrile. The solvent isevaporated and the residue dissolved in methylene chloride. Themethylene chlo ride solution is washed with water. dried. and evaporatedto afford. after recrystallization from 1- ehlorobutane. parts ofl-methyl-3-(tert-butyl)6- 24 methylthio-s-triazine-Z.4( lH 3H dione.

A solution ot'5 parts of the above material in parts of tetrahydrofuranat 0 is saturated with dimethylamine. The reaction is allowed to warm toroom temperature and stand overnight. The solvent is evaporated and theresidue triturated with ether to afford 4parts of lmeth vl-3-(tert-butyl o-dimethylamino-s-triazine- EXAMPLE 5 A. Preparation ofl-Methyl-3-cyelohexyl-o-methylthio-s-triazine- 2 4( lH.3H)-dione(Equations 6. 7. 8 9) To a solution of 56 parts of Z-methyl-Z-thiopseudourea sulfate in 300 parts of water at 0 are added dropwisesimultaneously 375 parts of methyl chloroformate and 62 parts of 50aqueous sodium hydroxide. The methyl chloroformate is added during 0.5hr and the 50% aqueous sodium hydroxide as required to keep the pH ofthereaction mass at 8.5. After the ad ditions are complete. the reaction isbrought to ambient temperature (2528) and held there for 2 hours.

To this suspension of l -c;irhomethoxy-Z-methyl-Z- thiopseudourea at2528 is added 300 parts of toluene. cyclohexyl isocyanate (44 parts) isadded over 0.5 hr and then stirred at 253() for an additional 2 hours.The toluene layer is then separated and 76 parts of a 25% sodiummethoxide solution is added. The solution is then refluxed for 1 hour(657()) and then a methanol-toluene mixture is distilled until a pottemperature of 88-90'is attained.

This toluene slurry of 3-cyelohexyl-o-methylthio-striazine-2.4( lH.3H)-dione sodium salt is then agitated with 650 parts of water for 0.15hrs. The aqueous layer is separated and reacted at 253() during 0.25 hrswith 57 parts of dimethyl sulfate. After the dimethyl sulfate is added.the pH of the reaction is maintained at pH 99.5 by addition of a totalof7.5 parts of 50% aqueous sodium hydroxide. The total reaction time isl.8 hrs at which time filtration and drying gives parts of whitel-methyl 3-cyclohexyl-6-methylthio-s-triazine- B. Preparation of l-Methyl-3-eyelohexyl-o-methylthio-s-triazine- 2 4( lH.3H)-dione(Equations 6a. 7a, 8, 9)

To a solution of 70 parts of 2-methyl-2- thiopseudourea sulfate in 375parts of water and 400 parts of toluene at 10 is added over 1 hour 62.5parts of cyclohexyl isocyanate. The pH is maintained at 8.5 by additionof parts of 50% aqueous sodium hydroxide over 1-1.5 hours. The two-phasesystem is then reacted with 99 parts of methyl chloroformate and 84parts of 5071 aqueous sodium hydroxide during 1 hour. The temperature ismaintained at 25-3(). After the addition is complete the reaction isstirred at 2528 for an additional 3 hours. The toluene layer isseparated and treated as in Example 5A to give 76 parts oflmethyl-3-cyelohexyl-o-methylthio-s-triazine-2.4- (lH.3H)-dione. m.p.l36l38.

C Preparation of l-Methyl-3-cyclohexyl-6-dimethylamino-s-triazine- 2.4(lH 3H)-di0ne (Equation 10) A suspension of 300 parts ofl-methyl-3-cyelohexyl- 6-methylthio-s-triazine-Z.4( lH 3H)-dione in 887parts (such as toluene). separating the solids (e.g. by filtration). andfurther extraction of the solids with the hydrocarbon solvent. followedby crystallization of the product from the hydrocarbon solvent extracts;or the reaction mixture can be treated with water. and the productextracted and crystallized as above.

The following example and Table 1X illustrate this procedure.

EXAMPLE 6 Synthesis ofl-Methyl-3-eyclohexyl-o-dimethylamino-s-triazine-4- thio-2.4( lH.3H)-dione To 25 parts ofl-methyl-S-cyelohexyl-fidimethylamino-s-triaZine-2.4-( lH.3H)-dione in200 parts of pyridine is added 45 parts of phosphorus pentasulflde. Themixture is refluxedfor 6 hours under a nitrogen atmosphere. The hotreaction mixture is diluted with 2511 parts of toluene and thesupernatent liquid decanted. The residue is mixed twice with 25(1-partportions of hot toluene and the supernatent liquid decanted. Thecombined supernatent liquid is concentrated to dryness and extractedwith hot toluene. The

hot extract is filtered. then cooled to give 18 parts ofl-methyl-3-cyclohcxyl-o-dimethylamino-s-triazine-4- thio-2.4( lH.3H)-dione. nip. 2 l()-2 12.

TABLE X Similarly the following 4-thio-s-triazinediones can be prepared.l-Mcthyl-3-cyclopentyl-o-dimethylamino-s-triaiine-4- thio-2 4(lH.3H)-dione. mp. l84.5-l86 l-Methyl-3-cyclooctyl (w-dimethylaminos-triazine-4- thio-2.4( 1H.3H )-dionel-Ethyl-3-cyclohexyl-o-dimethylamino-s-triazine-4- thio-2.4( 1H.3H)-dione l-Propy1-3-cyclohexyl-o-dimethylamino-s-triazine-4- thio-2.4(lH.3H)-dione l-Methyl- 3-phenyl-6-dimethylamino-s-triazine-4-thio- 2.4(lH.3H)-dione l-Methyl-3-norbornyl-(w-dimethylamino-s-triazine-4-thio-2.4( 1H.3H )'-dionel-Methyl-3-cyclohexylmcthyl-6-dimethylaminostriazine-4-thio-2.4( lH.3H)-dione1-Methyl-3-(Z-norbornylmethyl)-6-dimethylamino-striazinc-4-thio-2.4(1H.3H )-dione l-lsopropyl-3-eyclohexyl-o-dimethylamino-s-triazine-4-thio-2.4( 1H.3H )-dione 1-Methyl-3-cyclohexyl-6-( N-methyl-N-butyl)-6- dimethylamino-s-triazine-4-thio-2.4( 1H.3H )-dione Formulations andUse of the Compounds The compounds of formula 1 are useful for controlof undesired vegetation. They can be used Wherever general weed controlis required. such as industrial areas. railroad rights-of-way. and areasadjacent to croplands in agricultural areas.

The precise amount of (i-aminotriazinedione to be used in any givensituation will vary according to the particular end result desired. theuse involved. the plant and soil involved. the formulation used. themode of application. prevailing'weather conditions. foliage density. andlike factors. Since so many variables play a role. it is not possible tostate a rate of application suitable for all situations. Broadlyspeaking. the compounds of the invention are used at levels of about 1/2kilogram per hectare to about 25 kilograms per hectare. i

The compounds of formula 1 may be combined with other herbicides and areparticularly useful in combination with [3-( sec-butyl )-5-bromo-6-methyluracil diuron [3-(3.4-dichlorophenyl l .ldimethylurea paraquat (1,1-dimethyl-4,4- bipyridinium ion). m-(3.3-dimethylureido)phenyltertbutylcarbamate.4-amino-o-tert-butyl-3-methylthio-astriazine-5(4H)-one. and thes-triazines such as 2- chloro-4-ethylamino-6-isopropylamino-s-triazine.for controlling a broad spectrum of weeds.

The compounds of formula I can be formulated in the various ways whichare conventional for herbicides of similar physical properties. Usefulformulations include wettable and soluble powders. suspensions andsolutions in solvents and oils. aqueous dispersions. dusts. granules.pellets. and high strength compositions. Broadly speaking. theseformulations consist essentially of about 1 to 9971 by weight ofherbicidally active material (including at least one compound of formula1 in a .herbicidally effective amount) and at least one of a) about 0. 1to 2071 by weight of surface active agent and b) about 5 to 99% byweight of solid or liquid diluent. More specifically. the various typesof formulations will generally contain these ingredients in thefollowing approximate proportions.

' Y bromacil Percent by Weight High-Strength Compositions The actualpercentages that can be realized with a particular compound of formula 1will depend upon its physical properties.

The manner of making and using such herbicidal formulations is describedin numerous patents. See. for example. Luckenbaugh US. Pat. No.3.309.192. Loux US. Pat. No. 3.235.357. Todd US. Pat. No. 2.655.445.Hamm et al. US. Pat. No. 2.863.752. Scherer et al. US. Pat. No.3.079.244. Gysin et al. US. Pat. No. 2.891.855. and Barrous US. Pat. No.2.642.354.

Many of the compounds of this invention possess unusually highwater-solubility. up to several percent. This offers an advantage in.for instance. control of brush and other deep-rooted. perennial weeds.An example of a highly water-soluble compound of this invention isl-methyl-3-cyclohexyl-o-dimethylamino-striazine-2.4( lH.3H)-dione; thiscompound exhibits a solubility in water of about 3.2% at 25C.

EXAMPLE 7 Solution l-Methy1-3-cyclohexyl-6-dimethylamino-s- Water Theingredients are combined and stirred to produce a solution which can hetended with water for spra ingv (Si ly/urn: /l(I/('/Itll.\(') havingfour leaves. erahgrass and harn \ardgrass \\'ith three leaves andnutsedge \'pvru.\' rnlumlm) from tuhers with t\\'o leaves were treatedpostemergence at 2 2 kg per ha. Treated plants and EXAMPLE 8 5 controlsere maintained in the greenhouse for sixteen unable PUMIU. days. thenall species were compared to controls and llflcth l-Lgvclnpenhl-olim thl mimy \isuall rated for responses to treatment. A quantitatria/ine-2 4(lH..\H)-dione 35 the rating was made on a scale of 0 to l0: a rating ofDiatomaeeous earth 7|.5 r t t Dina) Hum sulrmuccimm 15 I mct ins omplctclull. a rating of 0 means no until I u\\\l\.0hll nieth \l cellulose 311) A qualitative rating type ol ll1 ]llt' was also made; the

letter indicates chlorosis. and the letter "(T indi- The ingredients arethoroughly blended and passed cates growth retardation. Ratings in thistest for some through a hammer mill to produce particles mostly allpreferred compounds of the invention follow:

Posleniergence ll'eelnergence Barn- Barn- Kg. .lohnsow ('rahard (ral\ard Compound Pei Hr. \utsedgc grass grass grass grass grass Sorghuml-|nelh l-3-isoprop l- -dinieth lamino- 2.2 l0(' l0(- l0(' l0(' l0('l0(' s-tria/ine-2.4( lH.3H l-dione 0.44 l0(' l0(' l0('methylamino-striazine2.4( lH.3H )-dione 0.44 10C l()(' I()( 10C 10C IUCbelow [00 microns. What is claimed is:

Herbicidal activity of compounds of this invention 1. Method ofcontrolling undesired vegetation which was discovered in a greenhousetest. In this test seeds comprises applying to the locus to be protecteda herbi- Of Crabgmss (Dlglturla PP-)- bilmyardgmss (EC/H710- cidallyeffective amount of a compound of the formula: clilou z'rusgulli). wildoats (Arena/hum). nutsedge i'- perusrotunu'us) Cass-[u mm. morningglory(lpomoea spp.) mustard (Brassiea spp. radish (Raphanus spp. N

N mangold (Tagetes spp.). dock (Rumex crispus), and l R 3 nutsedgetubers were planted in a growth medium and A treated preemcrgenee at tworates (2.2 and 0.44 kg. I R per ha.) with the chemicals dissolved in anon R wherein R is selected from alkyl ofZ through 8 carbon atoms,alkenyl of 3 through 6 carbon atoms, alkynyl of 3 through through 6carbon atoms. cycloalkyl of 4 through 8 carbon atoms, cycloalkenyl ofthrough 8 carbon atoms. cycloalkylmethyl of 4 through 9 carbon atoms,cycloalkenylmethyl of 6 through 9 carbon atoms, bicycloalkyl orbicycloalkenyl of 7 through carbon atoms and bicycloalkylmethyl orbicyeloalkenylmcthyl of 8 through 11 carbon atoms. trimethyleyclohexyland tetramethyleyclohexyl;

the above alkyl groups substituted with one methoxy,

ethoxy. methylthio or ethylthio group;

the above cycloalkyl groups substituted with one alkyl of 2 through 4carbon atoms, 1 through 2 methyl groups, 1 through 2 chlorines orbromines, one methoxy or one ethoxy group;

and

wherein I Q is hydrogen. fluorine, chlorine, bromine, alkyl of 1 through4 carbon atoms, alkoxy or alkylthio of 1 through 2 carbon atoms, nitroor a trifluoro methyl group. Y is hydrogen, chlorine, or methyl; and

Z is hydrogen or chlorine;

R. is hydrogen, alkyl of l through 3 carbon atoms or a cation selectedfrom Na*, Li", K (Ca/2V, ammonium and dimethylammonium;

R; is hydrogen, methyl or ethyl;

R, is alkyl of 1 through 4 carbon atoms, alkenyl of 3 through 4 carbonatoms, alkynyl of 3 through 4 carbon atoms. or methoxy; and

X is oxygen or sulfur;

provided that when X is sulfur, neither R nor R is hydrogen.

2. Method of claim 1 wherein:

R is alkyl to 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbonatoms. or cycloalkyl of 5 through 8 carbon atoms substituted with onemethyl group;

R R and R are methyl; and

X is oxygen or sulfur.

K 3. Method of claim 1 wherein:

Q R is alkyl of 3 through 6 carbon atoms; cycloalkyl of 5 through 8carbon atoms; cyclopentyl substituted i with one methyl group;cyclohexyl substituted with where P is hydrogen. methyl, chlorine. orfluorine.

and i Q is hydrogenor chlorine;

R R;;. and R, are methyl; and

X is oxygen. g

5. Method of claim 3 wherein:

R is alkyl of 3 through 4 carbon atoms; neopentyl; l-ethylpropyl;n-hexyl; cycloalkyl of 5 through 8 carbon atoms; Z-methylcyclohexyl; 3-methylcyclohexyl; 2.3-dimethylcyclohexyl; 3.4-dimethylcyelohexyl;2,4-dimethylcyclohexyl; 2,6-dimethylcyclohexyl; 3,5-dimethyleyclohexyl;

3-trifluoromethylphenyl; 3-cyclohexen-l-yl; or 1- decahydronaphthyl.

6. Method of claim 4 wherein:

R is 2,4-dimethyleyclohexyl; 2,6-dimethylcyclohexyl;2,3-dimethylcyclohexyl; 3,4-dimethylcyclohexyl; 3-trifluoromethylphenyl;3-cyclohexenl-yl; l decahydronaphthyl; phenyl; 3 methylphenyl:4-methylphenyl; 3,4-dichlorophenyl; 2.5- dichlorophenyl; Z-chlorophenyl;3-chlorophenyl; 4-chl0rophenyl; Z-fluorophenyl; 3-fluorophenyl;2-methyl-S-chlorophenyl; 0r 3-chloro-4- methylphenyl.

7. Method of claim 1 wherein:

R, is cyclopentyl, mcthylcyclopentyl, cyelohexyl, or

methyleyclohexyl;

R R3. and R are methyl; and

X is oxygen.

8. Method of claim 1 wherein the compound is:

l-Methyl-3-cyelohexyl-6-dimethylamino-s-triazine- 2,4( lH,3H)dione.

9. Method of claim 1 wherein the compound is:

l-Methyl-3-cyclopentyl-6-dimethylamino-s-triazine- 2.4( lH.3H)-dione.

10. A composition for controlling undesirable vegetation which comprisesat least one of (a) a surfactant and (b) an inert carrier material and acompound of the following formula:

wherein R is selected from alkyl of 2 through 8 carbon atoms. alkenyl of3 through 6 carbon atoms, alkynyl of 3 through through 6 carbon atoms,cycloalkyl of 4 through 8 carbon atoms, cycloalkenyl of 5 through 8carbon atoms, cyeloalkylmethyl of 4 through 9 carbon atoms,cyeloalkenylmethyl of 6 through 9 carbon atoms. bicycloalkyl orbicycloalkenyl of 7 through 10 carbon atoms and bicycloalkylmethyl orbicycloalkenylmethyl of 8 through ll carbon atoms, trimethyleyclohexyland tetramcthyleyclohexyl; the above alkyl groups substituted with onemethoxy,

ethoxy, methylthio or ethylthio group; the above cycloalkyl groupssubstituted with one alkyl of 2 through 4 carbon atoms, 1 through 2methyl groups, 1 through-2 chlorines or bromines, one methoxy or oneethoxy group; and

wherein Q is hydrogen. fluorine. chlorine. bromine. alkyl of I through 4carbon atoms. alkoxy or alkylthio of 1 through 2 carbon atoms. nitro ora trifluoromethyl group; Y is hydrogen. chlorine. or methy l; and Z ishydrogen or chlorine:

R. is hydrogen. alkyl of 1 through 3 carbon atoms or a cation selectedfrom Nai Li. Ki (Ca/2). ammonium and dimethylammonium.

R,, is hydrogen. methyl or ethyl.

R, is alkyl of I through 4 carbon atoms. alkcnyl of 3 through 4 carbonatoms. alkynyl of 3 through 4 carbon atoms or mcthoxy; and

X is oxygen or sulfur;

provided that when X is sulfur. neither R. nor R is hydrogen.

ll. Composition of claim 10 wherein:

R is alkyl of 3 through 6 carbon atoms. cycloalkyl of 5 through 8 carbonatoms. or cycloalkyl of 5 through 8 carbon atoms substituted with onemethyl group;

R R and R. are methyl; and

X is oxygen or sulfur.

l2. Composition of claim wherein:

R is alkyl of 3 through 6 carbon atoms; eycloalkyl of 5 through 8 carbonatoms; cyclopentyl substituted with one methyl group; cyclohexylsubstituted with l or 2 methyl groups; 3-trifluoromethylphenyl; cy-

clohexenyl; or decahydronaphthenl -yl'.

R and R are methyl;

R is hydrogen; and

X is oxygen.

13. Composition of claim 10 wherein:

R, is eyclohexyl substituted with two methyl groups;

3-trifluoromethylphenyl; dronaphthenl \'l'. or

where P is hydrogen. methyl. chlorine. or fluorine and Q is hydrogen orchlorine:

R R3. and R. are methyl; and

X is oxygen.

14. Composition of claim 12 wherein:

R, is alkyl of 3 through 4 carbon atoms; neopentyl; l-ethylpropyl;n-hexyl; cycloalkyl of 5 through 8 carbon atoms; Z-mcthylcyclohexyl; 3-mcthylcyclohcxyl; 2.3dimethylcyclohexyl; 3.4-dimethylcyclohexyl;2.4-dimcthylcyclohexyl; 2.6-dimethylcyelohexyl; 3.5-dimethylcyclohexyl;3-trifluoromethylphenyl; 3-cychohexen-l-yl; or ldecahydronaphthyl.

l5. Composition of claim 13 wherein:

R is 2.4-dimethylcyclohexyl; 2.6-dimethylcyelohexyl;2.3-dimcthylcyclohcxyl; 3.4-dimethylcyclohcxyl; 3-trifluoromethylphenyl;3cyclohcxenl-yl; l decahydronaphthyl; phenyl; 3 methylphenyl;4-methylphenyl; 3.4-dichlorophenyl: 2,5- dichlorophenyl; Z-chlorophenyl;3-chlorophenyl; 4-chlorophenyl'. Z-fluorophenyl; 3-fluorophcnyl;Z-methyl-S-chlorophenyl; or 3-chloro-4- methylphcnylv l6. Composition ofclaim 10 wherein:

R is cyclopentyl. methylcyclopentyl. cyelohexyl. or

mcthylcyclohexyl;

R R and R, are methyl; and

X is oxygen.

17. Composition of claim 10 wherein the compound cyclohexenyl; dccahyl-Methyl-3-eyclohexyl-6-dimethylamino-s-triazine- 2.4-( lH.3H)-dione. l8.Composition of claim 10 wherein the compound l-Methyl-3-cyclopentyl-6-dimethylamino-s-triazine- 2.4( 1H.3H )-dione.

1. METHOD OF CONTROLLING UNDESIRED VEGETATION WHICH COMPRISES APPLYINGTO THE LOCUS TO BE PROTECTED A HERBICIDALLY EFFECTIVE AMOUNT OF ACOMPOUND OF THE FORMULA:
 2. Method of claim 1 wherein: R1 is alkyl to 3through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms, orcycloalkyl of 5 through 8 carbon atoms substituted with one methylgroup; R2, R3 and R4 are methyl; and X is oxygen or sulfur.
 3. Method ofclaim 1 wherein: R1 is alkyl of 3 through 6 carbon atoms; cycloalkyl of5 through 8 carbon atoms; cyclopentyl substituted with one methyl group;cyclohexyl substituted with 1 or 2 methyl groups;3-trifluorometHylphenyl; cyclohexenyl; or decahydronaphthen-1-yl; R2 andR3 are methyl; R4 is hydrogen; and X is oxygen.
 4. Method of claim 1wherein: R1 is cyclohexyl substituted with two methyl groups;3-trifluoromethylphenyl; cyclohexenyl; decahydronaphthen-1-yl; or 5.Method of claim 3 wherein: R1 is alkyl of 3 through 4 carbon atoms;neopentyl; 1-ethylpropyl; n-hexyl; cycloalkyl of 5 through 8 carbonatoms; 2-methylcyclohexyl; 3-methylcyclohexyl; 2,3-dimethylcyclohexyl;3,4-dimethylcyclohexyl; 2,4-dimethylcyclohexyl; 2,6-dimethylcyclohexyl;3,5-dimethylcyclohexyl; 3-trifluoromethylphenyl; 3-cyclohexen-1-yl; or1-decahydronaphthyl.
 6. Method of claim 4 wherein: R1 is2,4-dimethylcyclohexyl; 2,6-dimethylcyclohexyl; 2,3-dimethylcyclohexyl;3,4-dimethylcyclohexyl; 3-trifluoromethylphenyl; 3-cyclohexen-1-yl; 1decahydronaphthyl; phenyl; 3 methylphenyl; 4-methylphenyl;3,4-dichlorophenyl; 2, 5-dichlorophenyl; 2-chlorophenyl; 3-chlorophenyl;4-chlorophenyl; 2-fluorophenyl; 3-fluorophenyl; 2-methyl-5-chlorophenyl;or 3-chloro-4-methylphenyl.
 7. Method of claim 1 wherein: R1 iscyclopentyl, methylcyclopentyl, cyclohexyl, or methylcyclohexyl; R2, R3,and R4 are methyl; and X is oxygen.
 8. Method of claim 1 wherein thecompound is:1-Methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione. 9.Method of claim 1 wherein the compound is:1-Methyl-3-cyclopentyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione. 10.A composition for controlling undesirable vegetation which comprises atleast one of (a) a surfactant and (b) an inert carrier material and acompound of the following formula:
 11. Composition of claim 10 wherein:R1 is alkyl of 3 through 6 carbon atoms, cycloalkyl of 5 through 8carbon atoms, or cycloalkyl of 5 through 8 carbon atoms substituted withone methyl group; R2, R3, and R4 are methyl; and X is oxygen or sulfur.12. Composition of claim 10 wherein: R1 is alkyl of 3 through 6 carbonatoms; cycloalkyl of 5 through 8 carbon atoms; cyclopentyl substitutedwith one methyl group; cyclohexyl substituted with 1 or 2 methyl groups;3-trifluoromethylphenyl; cyclohexenyl; or decahydronaphthen-1-yl; R2 andR3 are methyl; R4 is hydrogen; and X is oxygen.
 13. Composition of claim10 wherein: R1 is cyclohexyl substituted with two methyl groups;3-trifluoromethylphenyl; cyclohexenyl; decahydronaphthen-1-yl; or 14.Composition of claim 12 wherein: R1 is alkyl of 3 through 4 carbonatoms; neopentyl; 1-ethylpropyl; n-hexyl; cycloalkyl of 5 through 8carbon atoms; 2-methylcyclohexyl; 3-methylcyclohexyl;2,3-dimethylcyclohexyl; 3,4-dimethylcyclohexyl; 2,4-dimethylcyclohexyl;2,6-dimethylcyclohexyl; 3,5-dimethylcyclohexyl; 3-trifluoromethylphenyl;3-cychohexen-1-yl; or 1-decahydronaphthyl.
 15. Composition of claim 13wherein: R1 is 2,4-dimethylcyclohexyl; 2,6-dimethylcyclohexyl;2,3-dimethylcyclohexyl; 3,4-dimethylcyclohexyl; 3-trifluoromethylphenyl;3-cyclohexen-1-yl; 1 decahydronaphthyl; phenyl; 3 methylphenyl;4-methylphenyl; 3,4-dichlorophenyl; 2, 5-dichlorophenyl; 2-chlorophenyl;3-chlorophenyl; 4-chlorophenyl; 2-fluorophenyl; 3-fluorophenyl;2-methyl-5-chlorophenyl; or 3-chloro-4-methylphenyl.
 16. Composition ofclaim 10 wherein: R1 is cyclopentyl, methylcyclopentyl, cyclohexyl, ormethylcyclohexyl; R2, R3, and R4 are methyl; and X is oxygen. 17.Composition of claim 10 wherein the compound is:1-Methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione. 18.Composition of claim 10 wherein the compound is:1-Methyl-3-cyclopentyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione.